Polymeric detergents



Patented Nov. 23, 1948 POLEMERIC DETERGENTS Louis B. Bock, lluntingdon Valley, and James L. Rainey, Abington, 2a., assisnors to Bohm (a Haas Company. Philadelphia, 2a., a corpora;

tionof Delaware slmllcatlon September 9, 1944, Serial No. 553,418

hydrophilic groups or portions so arranged and balanced as tobecome oriented at an interface.

It is generally recognized that surface-active agents, as, for example, alkali-metal soaps or quaternary ammonium compounds, exist in water in the form of micelles. While the exact nature of such micelles is not established, there is evidence that they are. electrically charged aggregates of molecules. For example, when a sodium soap of a fatty acid is dispersed in water, it dissociates into positively charged sodium ions and into negative ions. Some of the latter apparently form aggregates with soap molecules and, as a result, negatively charged micelles are produced. Because the micelles carry a negative charge,- this type of soap is known as an anionactive detergent. In contrast, detergents of the type of quaternary ammonium compounds yield positively charged micelles in aqueous solution and, hence, are known as cation-active soaps or agents. This conception of the formation of micelles is based on measurements of freezing points, vapor pressures, and electrical conductivities of aqueous dispersions of surface-active agents. It is further recognized that surface activity is related to the formation of such micelles and to the orientation of the micelles at an interface.

The individual molecules in colloidal micelles are held together only by physical forces or by weak seondary valences; and, as a result, the extent of micelle formation depends upon the prevailing conditions, and it is affected by such factors as the concentration of the surface-active agent, the presence of electrolytes, solvents, and other surface-active agents, and also upon the temperature. Thus, dilution of the solution, elevation of the temperature, or a change in the amount or any salts which" may also be present in solution favor the reversion of micelles into simple molecules and/or ions with the formation of true solutions. As an example, synthetic detergents known heretofore have no value at very low concentrations or in very hot water because under these conditions the micellar structure reverts, themolecules then exist in true solution, and, as a result, detergency is lost. The neces sity of using relatively high concentrationsplus the higher cost of synthetic detergents combines to make the use of such detergents uneconomical andoiten impractical. Furthermore, the materials are ineffective in many laundering operations wherein extremely hot water is used in order to accelerate the removal of soil.

The products of this invention differ fromand have advantages over -detergents known heretofore in that their effectiveness is not dependent upon the formation of loosely bound micelles. By the process of this invention, water-soluble macromolecules are synthesized in which all of the bonds between atoms are primary valence links and, hence, are strong and are not afiected by such factors as concentration and tempera ture. Furthermore, the synthesized macromolecules contain balanced hydrophilic and hydrophobic groups so positioned in the macromolecule that orientation can and does occur readily at an interface.

The products of this invention may be made by condensing hydrocarbon-substituted phenols with formaldehyde to produce polymeric mate- 'rials which are in fact macromolecules and then introducing into said macromolecules hydrophilic groups. The hydrophilic groups, which impart water solubility, may be ether-alcohol groups or esterified ether-alcohol groups and are introduced, for example, by the reaction of ethylene oxideor a propylene oxide or a butylene oxide with the macromolecule. If desired, the terminal hydroxyl of said ether-alcohol group may be converted into a salt-forming ester group of a polybasic acid.

The resultant products may be considered to have three functional portions. Thus, they contain (a). as the hydrophobic portion, the hydrocarbon groups'attached to the phenol nucleus;

(b) as the hydrophilic portion, the modified or v unmodified ether-alcohol groups, and (c) as the polymeric portion, the phenol nuclei joined by methylene bridges. The hydrocarbon groups attached to the phenol and the modified or unmodified ether-alcohol groups alsov attached to the phenol are so balanced as to assure water solubility and orientation at an interface. At the same time, the polymeric nature of the product assures such a high molecular weight that the product is in fact a macromolecule which imparts capillaryor surface-activity to a solution,

as (lo-micelles of ordinary soaps, but which is stable and is not dissociated as are the micelles of customary detergents under adverse conditions.

The above discussion is for purposes of theoretical explanation only, and it must be understood that the so-called three portions of the macromolecule are not independent of each other but are all combined inone large molecule which functions as a concerted whole.

The type of hydrocarbon group which is attached to the-phenol nucleus may vary as to kind but in every case must contain at least four carbon atoms. In reality, substituting groups of at least eight carbon atoms are much preferred. Generally, it is preferred that the substituent hydrocarbon group be a straight or branched chain acyclic group, such as n-butyl, iso-butyl, tertiary butyl, amyl, tertiary amyl, n-octyl, diisobutyl, decyl, dodecyl, hexadecyl, octadecyl, and

the like. Alternatively, phenols substituted with alicyclic groups may be used. These are typified by cyclohexyl phenol, methyl-cyclohexyl phenol, butyl-cyclohexyl phenol, and dicyclohexyl phenol. While aryl-su'bstituted phenols, such as p-phenyl phenol and p-naphthyl phenol, may be employed they are less satisfactory than those listed above unless they in turn contain an alkyl group. Thus, p-toly-l phenol is much preferred over p-phenyl phenol. Furthermore, a preference is given to the para-substituted phenols over those substituted in the ortho position. It is understood that although it is preferable to employ individual phenols, mixtures of phenols, for example, p-tert.amyland p-diisobutyl-phenols, may be employed.

The ratio of formaldehyde should be between 0.5 and 1.0 mol per mol of phenol. 'I'he formaldehyde may be used in the form of a solution, such as the formalin of commerce, or in a polymeric form such as paraformaldehyde. Also, though not preferred, it may be in a form such as a formal 'or hexamethylene tetramine which will yield formaldehyde under the conditions of reaction. I

Ordinarily, the substituted phenol and formaldehyde are reacted by condensing together in the presence of an acidic or alkaline condensation catalyst until the products have become relatively viscous. Solvents may be employed. Acidic hydrocarbon-substituted phenoxy alcohols. They have the following general formula:

three. or four carbon atoms, 3 is zero'or an integer between one and twenty and preferably between one and seven, M is one equivalent of a metal, preferaibly of an alkali metal such as sodium, potassium, lithium, or a group 11 metal such as beryllium, magnesium, calcium, barium, or strontium, and a: is an integer greater than one.

These detergent products are preferably made by first reacting an alkali metal derivative of a hydrocarbon-substituted phenol-aldehyde polymer or macromolecule with a dihalogeno polyalkylene ether having the general formula, XR,-O-(RO)yR-X, in which X is a halogen, preferably chlorine, and R is an alkylene group, preferably of two to four carbon atoms,and y is zero or an integer. The reaction is conducted in the presence of a strongly alkaline condensing agent, such as sodium or potassium hydroxides, and only one'terminal halogen reacts with the sodium derivative of the macromolecule. In this way', substituted ether halides having the following general formula are produced:

condensation catalysts are preferred because of the ease with which the condensation may be controlled. Elevated temperatures naturally ac-- celerate the rate of reaction. Condensation of formaldehyde and substituted phenols such as are here involved does not proceed to the infusible stage and, accordingly, no limit need be imposed upon the degree of condensation. In practice, it is convenient to follow the extent of condensation by means of viscosity measurements and the condensation may be halted, at an early stage at which the molecular weight is low and the product This product is then heated with a water-soluble salt of sulfurous acid in aqueous or aqueous-alcoholic solution, and the final product has the general formula shown above.

Theldihalogeno polyalkylene others which may be used-are typified by thefollowlng: [MY-dichlorodiethyl ether, '-dibromodipropyl ether, p49- dichlorrodiisopropyl ether, fi-chloroethoxyethylp'-chloroethyl ether, and higher homologues.

The salts of sulfurous acid which are preferred are those of the alkali metals, especially of sodium, because these are water-soluble and most readily available.

As an alternative method, a polymeric condensate of a hydrocarbon-substituted phenol and formaldehyde may be condensed with 'an alkylene oxide, such as ethylene, a propylene oxide, or a butylene oxide, in the presence of an alkaline condensing agent. Preferably, more than one mol of oxide per mol of phenol in said condensate isused and, in such a case, the product is a Polymeric detergents in which the hydrophilic or water-solubilizing groups are alcohols or saltforming partial esters thereof are the subjects phenoxypolyalkoxy alcohol having the general formula:

- preparation of alcoholshaving' the above general formula is discussed in application Serial No.

553,476, filed of even date. It is possible to react on a steam bath, diluted with 250 milliliters of more than one moi of alkylene oxide per mol of benzene, and then washed with two portions of phenol in the macromolecule. In fact, as many 400 milliliters each of water. The product was as sixty have been reacted. However, a maxdried with anhydrous M03, and the benzene imum of twenty is indicated as satisfactory and and toluene were stripped off. A yield of 457 between one and eight is preferred. The terminal grams was bt of a product having a h1 hydroxyl group of the compound is next 0011- rine content of 7.68% and a hydroxyl number verted to a halide, for example, by reaction with of 11.

a halogenating agent such as phosphorous penta- Step 4.-A mlxtme of 396 grams of the product chloride, phosphorous o yc lo der thionyl of step 3, M0 grams .of sodium sulflte, and 800 chloride. The halide is then reacted with an grams of water was heated and stirred in an inorganic sulfite salt, such as sodium sulflte, to autoclave for four hours at 160-l7d C. The

yield a sulfonate. product, a turbid paste, was soluble in water and when measured asa 60% solution in toluene arid,

The products of this invention may be dewas surface-active in dilute aqueous solution. scribed as surface-active polymeric products of It had the following general formula:

on, t. aHu 8311 high molecular weight containing in their chem- Although the above example is directed to the ical structure a plurality of salt-forming hydrouse of ethylene oxide, it is understood that a carbon-substituted phenoxy-alkoxy sulfonate propylene oxide or a butylene oxide may be emunits joined through the nuclei of said phenoxy ployed in a similar manner. In order to impart groups by means of methylene bridges. a given degree of water-solubility, it is advisable Following is an example which indicates the to use a greater amount of the higher oxides than preferred method of preparing the products of the amount of ethylene oxide required. Furtherthis invention. more, as the entire length of the hydrophilic Step 1. -Into a three-necked flask equipped group is increased, the product ordinarily becomes with thermometer, mechanical agitator, and remore water-soluble. It is, therefore-advisable flux condenser was charged the following: 412 to increase the hydrophobic group proportiongrams of diisobutyl phenol, 162 grams of a 37% ately. This can be done by increasing the size of aqueous solution of formaldehyde, and 27.6 grams the hydrocarbon substituent of the phenol, as of water. The mixture was agitated and heated represented by R in the above general formula. to atemperature of 90 C. At this point, 2.46 Inthis way, a balance is maintained between the grams of oxalic acid and 0.92 gram of Twitchells hydrophilic and hydrophobic portions of the reagent dissolved in ten grams of water was added. macromolecule so that the product is water- While being agitated, the reaction mixture was 40 soluble and at the same time capillary-active, in refluxed for six hours. Two hundred grams of that it becomes oriented at an interface.

water and 384 grams of toluene were added, and All of the products of this invention function refluxing was continued for an hour. Agitation as capillary-active or, surface-active agents. As was stopped and the contents of the flask were such, they become oriented at an interface, lower removed to a separatory funnel. The aqueous thesurface tension of water, and cause more rapid and re ino l y wer parated and the solwetting of surfaces such as the surfaces of fibers ventwas removed from the re ino s l yer b as measured by the standard Draves Sinking vacuum distillation. After the removal of the t Their outstanding property is their eflecsolvent, heating at areduced pressure Of 1.5 13-) tiveness as detergents In this capacity as measat temperature 9 t %5- ured by wash tests and laundering tests, they are was confirmed for four and one'half hours' e outstanding and are. far superior to soaps and condensate then had a viscosity of 4.0 poises Synthetic detergents known heretofore.

As detergents the roducts described herein on cooling, solidified to a brittle mass. 1 may be used in hard gate! or in water of mgh eti ffini'n' i 232F232 22332125 8f aliment- Theymawbeemployedunderacwic g 1 weremixed with parts of toluene and or alkaline conditions. Their advantage over heated at 120L135, under pressure for t synthetic detergents resides in the fact that they hours. This ratio corresponds to three mols 6f g'ggflffiggigg g d g rffi ggm s ggl g gfigs gi fifi i igg ff 'ffififififig 1 13333? 60 are excellent detergents at very low concentration, was further diluted to 50% solids con tions or at very high temperatures where former with toluene. Its structure may be represented Synthetic detergents failed. as r n w 1 They are uncommonly advantageous in the 1Q sHn I 21111 I Step 3.To 934 grams of a solution prepared laundering of cotton fabrics and in the securing as, in step 2 was added 213 grams of benzyldiof wool, sized. dyed, and printed fabrics in genmethylamine and grams of thlonyl chloride. eral. They may be used for preparing disper- The reaction mixture was heated for two hours sions of oil in water or dispersions of polymer izable materials prior to the polymerization thereof. Also, they serve to break water-in-oil emulsions Such as are encountered in oil-fields. And they have been found to be very satisfactory in the treatment of leather, in the dispersion of pigments, and as assistants in dyeing.

The products of this invention are particularly useful when used in conjunction with other capillary-active agents, including fatty acid soaps and synthetic detergents such as those shown in United States Patents 2,115,192 and 2,143,759. Such combinations have extraordinarily high degrees of wetting and detergent properties.

We claim:

1. A modified phenol-formaldehyde condensation product having detergent properties wherein the phenol-formaldehyde condensate is an oily to brittle resinous condensation product of from 0.5 to 1.0 mol of formaldehyde and one mol of a phenol from the class consisting of ortho-substituted and para-substituted phenols, said phenol having the formula in which R is a saturated hydrocarbon substituent containing four to eighteen carbonatoms, and wherein the modification of said condensation product consists of the group 0.5 to 1.0 mol of formaldehyde and one mol of 'a phenol from the class consisting of ortho-substituted and para-substituted phenols, said phenol having the formula in which R' is a saturatethhydrocarbon substituent containing four to eighteen carbon atoms, and

wherein the modification of said condensation product consists of the group -(RO)'y-R,-SOaM replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said condensate through the phenolic oxygen atom thereof, wherein R in both occurrences is the same saturated alkylene group containing phenol from the class consisting of ortho-substituted and para-substituted phenols, said phenol having the formula inwhich R is a saturated hydrocarbon substituent containing eight to eighteen carbon atoms, and wherein the modification of said condensation product consists of the group 1 -(RO)y--RSO3M replacing the original phenolic hydrogen atoms and being attached to each phenol nucleous in said condensate through the phenolic oxygen atom thereof, wherein R in both occurrences is the same saturated alkylene group containing two to four carbon atoms, 31 has a value of 0 to 19 inclusive, and M is a metal from the class con- (RO)1IRSO3M replacing the original phenolic hydrogen atoms and being attached to each phenol nucleous in said condensate through the phenolic oxygen atom thereof, wherein R in both occurrences is the same saturated alkylene group containing two to four carbon atoms, :1; hasa value of zero to seven inclusive, and M is a metal from the class consisting of alkali and alkaline earth metals.

5. A modified phenol-formaldehyde condensation product having detergent properties wherein the phenol-formaldehyde condensate is an oily to' brittle resinous condensation product of from 0.5 to 1.0 mol of formaldehyde and one mol of aphenol from the class consisting of ortho-substituted and para-substituted phenols, said phenol having the formula OH v in which R is a saturated hydrocarbon substituent containing eight to eighteen carbon atoms, and wherein the modification of said condensation product consists vof the group replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said condensate through the phenolic oxygen atom thereof, wherein R in both occurences is the same saturated alkylene group containing two to four carbon atoms, 11 has a value of zero to seven inclusive, and M is an alkali metal.

6. A modified phenol-formaldehyde condensation product having surface-active properties wherein the phenol-formaldehyde condensate is an oily to brittle resinous condensation product of from'0.5 to 1.0 mol of formaldehyde and one mol of a phenol from the class consisting of orthosubstituted and para-substituted phenols, said phenol having the formula in which R'- is a saturated hydrocarbon substituent containing 4 .to 18 carbon atoms, and wherein '9 I the modification of said condensation pr'oduct consists of the group 4 r (C2H40) u Cal-I4 SOaM replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said condensate through the phenolic oxygen atom thereof, wherein g has a value of to 19 inclusive, and M is a metal from the group consisting of alkali and alkaline earth metals.

7. A modified phenol-formaldehyde condensation product having surface-active properties wherein the phenol-formaldehyde condensate is an'oily to brittle resinous condensation product of from 0.5 to 1.0 mol of formaldehyde and one mol of a phenol from the class consisting of ortho-substituted and para-substituted phenols, saidphenol having the formula in which a is a saturated hydrocarbon substituent containing 4 to 18 carbon atoms,and wherein the modification of said condensation product consists of thegroup Y (CzHaO) y Cal-I4 SOaM in which R is a saturated hydrocarbon substitu ent containing 4 to 18 carbon atoms, and wherein the modification of said condensation product consists of the group replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said condensate through the phenolic oxygen atom thereof, wherein g; has a value of 0 to 19 inclusive,

and M is a metal from the group consisting of alkali and alkaline earth metals.

9. A modified phenol-formaldehyde condensation product having surface-active properties wherein the phenol-formaldehyde condensate is an oily to brittle resinous condensation product of from-0.5 to 1.0 mol of formaldehyde and one mol of a phenol from the class consisting of ortho-substituted and para-substituted phenols, said phenol having the formula in which R is a saturated hydrocarbon substituent containing 4 to 18 carbon atoms, and wherein the modification of said condensation product consists of the group (CaHaO) 1 C4Ha $03M replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said condensate through the phenolic oxygen atom thereof, wherein y has a value of 0 to 19 inclusive, and M is a metal from the group consisting of alkali and alkaline earth metals.

10. A modified phenol-formaldehyde condensation product having surface-active properties wherein the phenol-formaldehyde condensate is an oily to brittle resinous condensation product of from 0.5 to 1.0 mol of formaldehyde and mol of a phenol having the formula and wherein the modification consists of the group (C2H4O) u C2H4 SOaNa replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said condensate through the phenolic oxygen atom thereof, wherein 11 has a value of 0 to 19 inclusive.

LOUIS H. nocK. JAMES L. RAINEY.

REFERENCES CITED The following references are of record in the file of this patent:

I UNITED STATES PATENTS Number Name Date 2,046,318 Brubaker July 7, 1936 2,178,829 Bruson et'al. Nov. 7, 1939 2,213,477 Steindorfi et a1. Sept. 3, 194d FOREIGN PATENTS Number Country Date 576,177 Germany .1.- May 8, 1933 one - I Certificate of Correction 7 Patent No. 2,454,543. November 23, 1948.

. LOUIS H. BOOK ET AL. Y

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 4, in the formula following line 2, right-hand portion thereof, for O(RO),SO M read 0(R0),,R-S0 M; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Ofiice.

. Signed and sealed this 5th day of April, A. D. 1949.

THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

